Ethers of glycol mono-aryloxyacetates



UNITED STATES PATENT OFFICE ETHEBS F GLYCOL MONO-ABYLOXY- ACETATES Ernest F. Grether, Midland, Micln, assignor to The Dow Chemical Company, Midland, Mich, "a corporation oi. Michigan No Drawing. Application December 4, 1936,

Serial No. 114.229

11 Claims. (Cl. 106-40) The present invention concerns ethers of glycol tion of certain of our new ether-ester compounds monoaryloxy-acetates and plastic compositions and plastic compositions comprising the same,

comprising the same. but are not to be construed as limiting the inven- I have found that the ethers of the glycol tion. mono-aryloxy-acetates are viscous, water-white Example 1 liquids, or low melting solids and that they are particularly valuable as plasticizers for cellulose acetic acid and 100 rams (1 31 mols) of meth derivatives by virtue of their high boiling points, oxwethanol, L e. moimmethyl ether Methylene low volatilities, insolubility in water, and resistglycol, and 4 grams of benzene sulfonic acid was ance to hydrolysis, decomposition by heat, and heated to a temperature of C. water was 10 discoloration light" distilled out of the reaction zone as formed in the The inventwn thel cnslsts in the new reaction and the heating continued to 100-108 pounds and oomposltlons comprising the some 0. for approximately 3 hours, i. e. until water hereinafter described and particularly pointed vapor was no longer evo1ved The reacted out In the q t-ure was then washed with water and iractionally 1 The herein descrlbed ethers of E mono distilled, whereby there was obtained 183 grams aryloxv-eceietes may be P e by heating a (0.87 mol) of the methyl ether of ethylene glycol mixture of an aryloxy-acetic acid and a glycol monmphenoxymcetate as a water white liquid mono-ether. to a temperature at which reaction boiling at l37-138 c. at 3 millimeters pressure,

occurs, and thereafter separating the ether-ester and having th specific gravity 1.144 at 20/4 C. m

product from the reacted mixture, e. g. by fractional distillation, crystallization, etc. The arylxample 2 D di-a e c acid and 8 3 mono-ether may b In a similar manner 608 grams (4.0 mols) of emp y d in a y d s r d pr rt ns, alth u phenoxy-acetic acid, 450 grams (5.0) mols of 26 I generally employ a molar excess of the glycol 'ethoxy-ethanol, and 8 grams of benzen'esulfonic mono-ether. The reaction proceeds most acid were reacted together at a temperature of smoothly and rapidly at temperatures between 110-133 C. over a period of 4"hours. Upon 100 and 180 C. but may be carried out at somefractional distillation of the crude reaction mixwhat lower or higher temperatures, if desired. ture, there was obtained 800 grams (3.57 mols) 30 During the reaction water vapor is evolved, which of the ethyl ether of ethylene glycol mono-pheis removed from the reaction zone. For 0011- noxy-acetate as a water white liquid boiling bevenience the reaction is usually carried out at tween 130 and 135 C. at 2 millimeters pressure, atmospheric or slightly higher pressure, but may and having a specific gravity of 1.111 at 20/4 C. also be carried out with advantage under vacuum Ema l 3 to facilitate the removal of water from the mixmp e 85 ture, whereby a more rapid and complete reac- 4 grams (3-0 mols) of phenoxy-acetic a id. tion may be obtained. Ordinarily the reaction is 375 grams H1015) 0f b yo and 6 substantially complete in about 2 to 10 hours unr ms of benzene sulfonic acid were mixed toder the conditions above described. gether and heated at temperatures gradually in- In a modification of this method the ethers of creasing from 135 C. to 145 C. over a p o 0f 0 the glycol mono-aryloxy-acetates may be pre- 2 hours, water being removed from the reaction pared by reacting together an aryloxy-acetic id zone as formed. Fractional distillation of the and a glycol substantially as described to form a reacted mixture resulted in the co e y of 36 glycol-mono-aryloxy-acetate and thereafter grams of unreacted phenoxy-acetic acid and the etherifying said mono-acetate product with an isolation of 623 grams (2.51 mols) of the butyl alcohol, phenol, etc. ether of ethylene glycol mono-phenoxy-acetate If desired, a catalyst such as an inorganic acid, as a free-flowing liquid boiling at 138-139 C. at e. g. sulphuric acid; acid salt, e. g. sodium acid 3 millimeters pressure, and having a specific su phate; aromatic sulphonic acids, etc., may be I gravity of 1.063 at 20/4 C. employed in the above method to promote rapid A mixture of 152 grams (1.0 mol) of phenoxyreaction at relatively low temperatures, but the Emmp 1e 4 reaction proceeds smoothly and rapidly in the 93 grams mol) of r -p -a i absence of such catalysts under the conditions d wa r ac with '75 grams (0.83 mol) of described above. ethoxy-ethanol in the presence of 1 gram of ben- 5 The following examples describe the preparazene sulfonic acid. Thereaction mixture was Example 5 A mixture of 88 grams (0.58 moi) of phenox'yacetic acid, 100 grams (0.58 mol) of the 2-chlorophenyl ether of ethylene glycol, and 5 grams of benzene sulfonic acid was maintained at a reaction temperature of l30-160 C. for 2 hours, substantially as described. The reaction mixture was thereafter poured into an excess of 95 per cent ethyl alcohol, whereby the desired ester product was precipitated. The precipitate was separated by filtration, washed with cold ethyl alcohol, and air-dried. 135 grams (0.44 mol) of the 2-chloro-phenyl ether of ethylene glycol mono-phenoxy acetate was thereby obtained as a white crystalline solid having a melting point of approximately 44 C.

Other mono-ethers of the glycols may be substituted for those shown in the examples to form compounds such as the phenyl ether of propylene glycol mono-phenoxy-acetate, the benzyl ether of ethylene glycol mono-2-chloro phenoxy-acetate, the cyclohexyl ether of butylene glycol mono-phenoxy-aoetate, etc. In a similar manner other aryloxy-acetic acids may be employed in the reaction whereby there are formed compounds such as the ethyl ether of ethylene glycol mono-2-phenyl phenoxy acetate, the 2-chlorophenyl ether of ethylene glycol mono-orthocresoxy-acetate, the ethyl ether of ethylene glycol mono-betal-naphthoxy-aoetate, etc. By substituting mixtures of reactants for the pure compounds employed in the examples, mixtures of ether-ester derivatives of the glycols may be obtained as permanent liquids, compatible with cellulose derivatives, readily soluble in the common organic solvents. and having low-volatilities.

The following examples illustrate the use of the ethers of glycol-mono-aryloxy-acetates in cellulose derivative compositions:

Example 6 11 parts by weight of an ethyl cellulose having a 47.5 per cent ethoxy content, and 7 parts by weight of ethyl ether oi. ethylene glycol monophenoxy-acetate were dissolved in 82 parts of a solvent mixture consisting of 67 per cent of benzene and 33 per cent of ethyl alcohol by volume. A foil 0.026 inch thick was cast from' ,this solution on a continuous belt in a film casting machine. This foil, containing approximately 40 per cent by weight of the ether ester plasticizer, was highly flexible, retaining its fiexibility at low temperatures, and being adapted for use in producing a laminated safety glass.

Example 7 Films of ethyl cellulose were prepared, some containing up to 15 per cent by weight of the ether of ethylene glycol mono-phenoxy-acetate and others an equivalent amount of the ethyl ether of ethylene glycol mono-Z-chloro-phenoxyacetate. These films showed no yellowing effect after a 72-hour exposure to the light from a carbon arc in a standard testing apparatus known as a "fadeometer.

Mono-methyl ether of ethylene glycol..--- 9 Methyl ether of ethylene glycol monophenoxy acetate... 3.3 This composition was employed in the preparation of clear foils of excellent flexibility.

Example 9 8 parts of ester gum, 10 parts of one-half second nitro-cellulose. and 4 parts of the ethyl ether of ethylene glycol mono-phenoxy acetate were dissolved in 78 parts of a solvent mixture consisti of:

Parts Toluene 54.6 Ethyl acetate 11.7 Ethyl al 3.9 Glycol mono-ethyl ether 3.9 Methyl ether of ethylene glycol acetate.. 3.9

This composition was found suitable as a lacquer for spray application.

Example 10 Rolls cast from a composition consisting of:

Parts Benzyl cellulos 1 Ethyl ether of ethylene glycol mono-orthochloro-phenoxy acetate Toluene 67 Butanol 9 Butyl aceta 9 were found to be flexible and soft in nature and to have desirable adhesive characteristics. Substitution of 2.5 parts of the ortho-chloro-phenyl ether of ethylene glycol mono-phenoxy acetate for the 5 parts of the ethyl ether of ethylene glycol mono-ortho-chloro-phenoxy acetate, as

shown above, resulted in a composition from i which flexible foils of increased hardness were likewise prepared.

Ezample 11 parts of titanium dioxide was suspended in a solution consisting of Pm. Benzene 20.1 Methan l 9.9

Ethyl ether of ethylene glycol mono-phenoxy aceta e 100 parts of ethyl cellulose was thereafter incorporated with the suspension and carefully kneaded to secure good dispersion of the pigment and plasticizer therein. The resulting mixture was then freed of solvent on calender rolls and the sheet obtained thereby formed into plastic shapes in the usual manner.

Cellulose derivative compositions containihg other ethers of the glycol mono-aryloxy-acetates may be prepared in a like manner and employed- I, therefore, particularly point out and distinctly claim as my invention:-

l. A plastic composition comprising a cellulose derivative and an ether of a glycol mono-aryloxyacetate.

2. A plastic composition comprising a cellulose derivative and an ether of an ethylene glycol mono-aryloxy-acetate.

3. A plastic composition comprising a cellulose ether and an ether of an ethylene glycol monoaryloxy-acetate.

4. A plastic composition comprising a cellulose ether and an alkyl ether of an etlurlene glycol mono-aryloxy-acetate.

5. A plastic composition comprising a cellulose ether and an ethyl ether of an ethylene glycol mono-aryloxy-acetate. A

8. A plastic composition comprising ethyl cellulose and an ether of a glycol mono-aryloxyacetate.

7. A plastic composition comprising ethyl cellulose and an ether of an ethylene glycol monoaryloxy-acetate.

8. A plastic composition comprising ethyl cellulose and an alkyl ether of an ethylene glycol mono-aryloxy-acetate.

9. A plastic composition comprising ethyl cellulose and an ethyl ether of an ethylene glycol mono-aryloxy-acetate.

10. A plastic composition comprising ethyl cellulose and an ether of ethylene glycol mono- 

